化工学报 ›› 2023, Vol. 74 ›› Issue (3): 1102-1112.DOI: 10.11949/0438-1157.20221442

• 催化、动力学与反应器 • 上一篇    下一篇

Cu/Co掺杂多孔炭活化过硫酸盐降解水中硝基酚研究

闫新龙1(), 黄志刚1, 胡清勋2, 张新1, 胡晓燕1   

  1. 1.江苏省碳资源精细化利用工程研究中心,中国矿业大学,江苏 徐州 221116
    2.中国石油兰州化工研究中心,甘肃 兰州 730060
  • 收稿日期:2022-11-07 修回日期:2023-02-20 出版日期:2023-03-05 发布日期:2023-04-19
  • 通讯作者: 闫新龙
  • 作者简介:闫新龙(1983—),男,博士,副教授,yanxl@cumt.edu.cn
  • 基金资助:
    徐州市重点研发计划(社会发展)项目(KC20196);国家自然科学基金项目(21606252)

Catalytic nitrophenol degradation via peroxymonosulfate activation over Cu/Co doped porous carbon

Xinlong YAN1(), Zhigang HUANG1, Qingxun HU2, Xin ZHANG1, Xiaoyan HU1   

  1. 1.Jiangsu Province Engineering Research Center of Fine Utilization of Carbon Resources, China University of Mining and Technology, Xuzhou 221116, Jiangsu,China
    2.Lanzhou Petrochemical Research Center, PetroChina, Lanzhou 730060, Gansu,China
  • Received:2022-11-07 Revised:2023-02-20 Online:2023-03-05 Published:2023-04-19
  • Contact: Xinlong YAN

摘要:

以MOF-74为模板制备了Cu/Co双金属掺杂多孔炭催化剂。用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、N2物理吸附/脱附等对催化剂结构进行了表征。研究并阐释了Cu/Co双金属掺杂多孔炭催化剂活化过一硫酸盐(PMS)氧化降解4-硝基酚性能及机理。结果表明,在投加100 mg·L-1催化剂、2 g·L-1 PMS、初始pH为6时,15 min内硝基酚(60 mg·L-1)去除率达98%以上。降解反应符合伪一级反应动力学模型。催化剂循环反应4次,降解率均高于90%。猝灭实验及电子顺磁共振分析表明自由基(·SO4-、·OH、·O2-)和非自由基(1O2)均参与了降解反应。在反应过程中,Co2+/Co3+和Cu+/Cu2+的氧化还原循环有效活化了PMS并促进活性氧化物种的生成,从而提升了催化剂降解硝基酚的性能。

关键词: 氧化, 催化剂, 废水, 过硫酸盐, 硝基酚

Abstract:

Carbon-based catalysts with heteroatom doping and porous structures are desired for advanced oxidation processes (AOPs). Herein, Co and Cu co-doped porous carbon were developed by using metal-organic frameworks-74 (MOF-74) as self-sacrificial template and performing subsequent carbonization. The obtained samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), et al. The optimal composite catalyst (Cu1Co1-OC) exhibited excellent catalytic degradation performance toward 4-nitrophenol (4-NP). More than 98% of 4-NP (60 mg·L-1) could be removed within 15 min by 100 mg·L-1 of catalyst and 2 g·L-1 of peroxymonosulfate (PMS) at pH=6. Moreover, the catalyst showed good stability and reusability with about only 10% efficiency loss after 4 cycles. The effects of catalyst and PMS dose, pollutant concentration, pH and common anions were investigated, and reactive oxygen species (ROS) were studied by scavenger experiments and electron paramagnetic resonance (EPR) tests. Quenching experiments and electron paramagnetic resonance analysis showed that both free radicals (·SO4-, ·OH, ·O2-) and non-free radicals (1O2) participated in the degradation reaction. During the reaction process, the redox cycle of Co2+/Co3+ and Cu+/Cu2+ effectively activated PMS and promoted the generation of active oxide species, thereby improving the performance of the catalyst for the degradation of nitrophenols.

Key words: oxidation, catalyst, waste water, peroxymonosulfate, 4-nitrophenol

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